Black sulfur dye.



' UNITED STATES PATENT OFFICE.

I JULIUS ABEL AND FRITZ KALKOW, OF LUDWIGSHAFEN, GERMANY, ASSIGN- ORS TO THE BADISCHE ANILIN AND SODA FABRIK, OF SAME PLACE.

SPECIFICATION forming part of Letters Patent No. 650,293, dated May 22, 1900.

Application filed March 13, 1900. Serial No. 8,473. (No specimens.)

To all whmmit may concern:

Be it known that we, JULIUS ABEL, doctor of philosophy, a citizen of the free Hansa town of Hamburg, and FRITZ KALKOW, doctor of philosophy, a subject of the King of Prussia, Emperor of Germany, both residing at Lud- Wigshafen-on-the-Rhine, in the Kingdom of Bavaria and Empire of Germany, have invented new and useful Improvements in Black Coloring-Matters, of which the following is a specification.

Our invention relates to the production of black coloring-matter, with a green cast, directly dyeing cotton, which can be obtained by heating certain diphenylamin derivatives with sulfur and an alkaline sulfid. The said diphenylamin derivatives can be obtained, as we have discovered, by heating one molecular proportion of a para-hydroXy-ortho-paradinitro-diphenylamin body-such, for example, as the condensation product of meta-db nitro chlorbenzene and para-amido-phenol (which is described by Nietzki and Simon, Berichte der Deutschen Uhemischen GeseZZ- schaft, 1895, p. 2973) or para-amido-phenolortho-sulfoacidwith one molecular propor-' tion of meta-dinitro-chlorbenzene, for example, in aqueous solution in the presence ofabout one molecular proportion of carbonate of soda or caustic soda. If preferred, however, the intermediate condensation product I so,n I a o No o no,

and are accordingly derivatives of nitrated phenol ethers. Other similar phenol-ether derivatives which are suitable as initial ma terial for the manufacture of our new colorin g-matters can be obtained by heating parahydroxy-ortho-para-dinitro-diphenylamin derivatives with ortho-nitro-chlorbenzene-para sulfoacid or with para-nitro-chlorbenzeneortho-sulfoacid. These bodies would presumably have the constitution indicated by the following formulae:

- with-or without the SO H group inclosed in brackets.) I v The shades which our new coloring-mat ters' give are black, with a greenish cast characterized by considerable beauty and excel lent .fastness. Treatment with bichromate and sulfuric acid in the well-known manner renders them bluish black. The following example will serve to illustrate the nature of our invention and how it may be carried into practical efiect. Thewparts are by weight.

' Production ofanew black c0Z0m'ng-matter. Mix together about forty (40) .parts .of the sodium salt of para-dinitro-phenoxy-orthopara dinitro diphenylamin meta sulfoacid with eighty (80) parts of sulfur and two hundred (200) parts of crystallized sodium sulfid. Heat this mixture in an iron pot furnished soap.

with a stirrer at a temperature of about 140 centigrade.- When the mass no longer froths up, but turns solid, the reaction may be regarded as ended. Allow to cool and reduce it to-powder. This powder can be directly used fondyeing. L

In a similar-manner coloring-matters are obtained from the other new condensation'products hereinbefore indicated. Of course the conditions of working-such as the temperature of melting, can be varied in all cases Without departure from the nature of curinvention.

Our new coloring-matter,which can be thus obtained, is"a dark powder readily soluble in water, giving a bluegreen solution, from which common salt andjamm'oniuni chlorid precipitate blue -'green flocks-1v On'unmordanted cotton our. new coloring-matter pr0- duces green-black shades, whichpossess extraordinary fastness to acids, alkalies, and Upon treatmentwith bichromate and sulfuric acid beautiful bluish-black shades are obtained, which resist to an excellent degreethe action of soap, chlorin, and sulfur di= oxid. i i' Now what We claim is.-

As a new product the dyestuff which can be obtained by treating a specified diphenyL' amin derivative with sulfur andsodium sul-- 'fid, which coloring-matter issoluble in water with a blue green color, and is precipitated from this solution by common saltin bluegreen, flocks and dyes unmordanted cotton in green-black shades of great fastness to acids, alkaliesandsoap, which ontreatment with bichromate and sulfuric acid are turned blueish-black and resist to a high degree the action of soap, chlorin and sulfur dioxid.

In testimony whereof we have hereunto set our hands in the presence oftwo subscribing witnesses.

JULIUS ABEL. FRITZ KALKOl/V. 

